Composition containing organosiloxane and polyimine and method of treating textiles therewith



Unite COMPOSITION CONTAINING ORGANOSILOXANE AND POLYIMINE AND METHOD OFTREATING TEXTILES THEREWITH No Drawing. Application January 26, 1956Serial No. 561,665

6 Claims. (Cl. 26029.2)

This invention relates to a substantive method for applying siloxanes tofabrics.

This application is a continuation-in-part of applicants copendingapplication Serial No. 550,218, filed November 30, 195 5, now abandoned.

.Prior to this invention siloxanes were generally applied to fabrics byimmersing the fabric in an emulsion until it was thoroughly wet andthereafter removing the fabric from the emulsion and drying to cure thesiloxane.

In heretofore employed methods this was usually done continuously andthe amount of 'siloxane deposited on the fabric was dependent upon theamount of siloxane in the emulsion which was actually retained by thefabric as it emerged from the bath. That is, the amount of siliconepicked up by the fabric was determined solely by the concentration ofthe siloxane in the treating emulsion. There was little preferentialadsorption of the siloxane on the fabric surface. Consequently thefabric was passed through the emulsion until the emulsion was completelyremoved from the container.

Whereas this method works satisfactorily. for continuous operation itdoes not work satisfactorily for batch operations. This is true becausethe batch of fabric would be dipped into the emulsion and thereafterremovedand dried. Under such conditions only a fraction of the siloxanein the treating bath would be deposited on the fabric. As is well known,siloxane emulsions containing SiH compounds are not stable. Thesematerials are the ones most commonly employed on fabrics. As a result,for batch operations, much of the silox ane would be wasted due to thegelling of the emulsion or for other causes.

There are many types of fabrics such as knit goods which cannot becontinuously passed through an emulsion. Furthermore, it is oftendesirable to treat finished garments such as sweaters, blankets, orhosiery. These cannot conveniently be treated continuously but must betreated by batch process, that is, a process in which any one batch ofemulsion is employed to treat a limited number of pieces of fabric orgarments. It would be highly desirable, therefore, to have a system fromwhich all of the siloxane in the emulsion treating bath would becompletely adsorbed on the surface of the fabric Within a reasonablelength of time. In such a system there would be no waste of the siloxaneand one could employ muchmore dilute emulsions than has heretofore beenpossible in treating fabrics.

It is the object of this invention to provide a novel method forapplying siloxanes to fabric in which the siloxane is preferentiallyadsorbed on the surface of the fabric. Another object is to provide amethod for treating fabrics by a batch process. Another object is toprovide a method which would be applicable to a wide'variety ofsiloxanes and to all types of'fabrics. Other objects and advantages willbe apparent from the following description.

This invention relates to a method of depositing a siloxane on a fabricwhich comprises immersing the tates Patent fabric in a siloxanein-wateremulsion containing a nonionic emulsifying agent and from .2 to byweight based on the weight of the siloxane of a nitrogen compound of thegroup polyimines of the formula in which Z is of the group NH orhalogen, R is hydrogen or methyl and x is an integer of at least 4,salts of said polyimines and compounds of the formula in which R" is analiphatic hydrocarbon radical of less than 5 carbon atoms, Y is an acidanion and n has a .value of at least 2 and thereafter removing thefabric from the water and drying.

The substantative agents employed in the method of this invention arethe polyimines and salts thereof and the defined quaternary ammoniumpolyglycols. These materials cause a spontaneous deposition of thepolysiloxane in the emulsion on the surface of the fabric. In general,the silox-ane is completely adsorbed in less than 60 minutes andgenerally in less than 15 minutes. The adsorption of the siloxane isindicated by a clearing of the emulsion. This may be measured by lighttransmission. When the transmission through the treating bath reachesall of the siloxane has been deposited on the fabric.

The concentration of the siloxane in the emulsion in the process of thisinvention is not critical. However, for practical operation, it ispreferred that the emulsion be fairly dilute. Ideally the amount ofsilicone in the emulsion should be that which will give the desiredpickup on the fabric. Thus if one desires a 2% weight pickup of siloxaneon the fabric the amount of siloxane in the emulsion should be 2% byweight of the weight of the fabric being treated. It should beunderstood of course that the process of this invention is not limitedto those cases in which the siloX-ane is completely exhausted from thebath in any one operation. This invention also includes the type ofoperation in which successive batches of fabric are treated from a moreconcentrated emulsion.

For example, an emulsion containing say 10% by weight silicone, based onthe weight of the fabric to be treated in any one batch, can be employedto treat five batches of fabric in which a 2% pickup is desired, on allthe fabric. The first batch was allowed to remain until 2% pickup wasobtained. It can then be removed and a second batch immersed and allowedto remain until 2% pickup is again obtained. This process can berepeated until the bath is entirely exhausted.

The amount of siloxane applied to the fabric is not critical although ithas been found in general that the surface becomes saturated at about 3%by weight siloxane based upon the weight of the fabric.

It has been found that the method of this invention can be carried outat any desired pH. Obviously extremely acidic or basic conditions shouldbe avoided so as not to damage the fabric. The preferred pH range isfrom 2 to 10. This is a decided advantage over most substantivetreatments which are quite sensitive to pH.

SiloXanes employed in this invention can be any emulsifiable siloxane ofthe formula in which R is any monovalent hydrocarbon radical, anyhydroxylated'monovalent hydrocarbon radical or hydrogen and m has anaverage value from 1 to 3 inclusive. It is preferred that at least 50%of the R groups in the siloxane be an organic radical.

For the purpose of this invention the siloxane can range from viscousresins to thin fluids. It should be understood that the siloxane can beany homopolymer or copolymer and may contain any combination of siloxaneunits of the formula RSiO R SiO and R SiO together with limited amountsof SiO units.

For the purpose of this invention R can be any monovalent hydrocarbonradical such as alkyl radicals such as methyl, ethyl, butyl andoctadecyl; alkenyl radicals such as vinyl, allyl and hexenyl;cycloaliphatic radicals such as cyclohexyl and cyclohexenyl; arylhydrocarbon radicals such as phenyl, xenyl, tolyl and naphthyl andalkaryl hydrocarbon radicals such as benzyl. R can also be anyhydroxylated hydrocarbon radical such as gamma-hydroxypropyl,5-hydroxybutyl, hydroxycyclopentyl, hydroxycyclohexyl, hydroxyphenyl,3-hydroxymethyl-Z-methylcyclohexyl 6%0 H CH2 Siloxanes containing theabove hydroxylated radicals can be prepared in accordance with themethod of the copending application of John L. Speier, Serial No.463,061, filed October 18, 1954, now abandoned.

The substantive agents employed in the method of this invention can bepolyirnines derived from ethylenediamine and propyleuediamine. Thesematerials can be prepared by the polymerization of ethylene imine orpropylene imine and lllfle (i. e. OHzCHz and CHCHI) or they may beprepared by the condensation reaction of ethylenediamine orpropylenediamine with an ethylenedihalide or a propylenedihalide. In thelatter reaction the hydrogen halide evolved reacts with the amino groupsto form the imine hydrohalide. Also in this reaction if the dihalide isused in excess some residual halogen atoms will remain on the ends ofthe molecules. All of these materials are within the scope of thisinvention provided there is at least 4 alkylene imine units permolecule.

Specific examples of operative imines are those of the formula Cl(CH CHNH) CI-I CH CL hl/[e NHn CHCHzNIDaH Me 1.301 Me C1(CHCHzNH)5CHCH2Cl asmethyl, ethyl, vinyl, propyl, allyl, butyl and isopropyl. For thepurpose of this invention the Y group in the salt can be any acid anionsuch as chloride, bromide, iodide, nitrate, sulfate, acetate, formate,propionate and the like. The salts other than the halides are bestprepared by ion exchange with the corresponding halide salts.

The emulsifying agents employed in the process of this invention must beof the non-ionic type. Any nonionic emulsifying agent may be employedsuch as, for example, alkyl ethers of polyalkylene glycols such aspolypropylene glycol monobutyl ether, polyethylene glycol 2-ethylhexylether and polyethylene glycol monobutyl ether and esters of polyhydricalcohols such as glycerol monostearate, polyoxyethylenedistearate andpropylene glycol monolaurate. The amount of emulsifying agent is notcritical but it is usually employed in amount less than 50/21 based onthe weight of the siloxane.

Preferably the emulsion should contain a catalyst for setting thesiloxane. For this reason one may employ water soluble titanates such astriethanolamine titanate, diethanolamine titanate, triethanolaminezirconate and salts such as sodium acetate, zinc acetate and the like.

It has been found that in the treatment of wool fabrics the alkanolamine titanates are of particular utility as catalysts. This isparticularly true when the siloxane has hydrogen bonded to at least someof the silicon atoms. The use of the combination of the substantiveagents and the alkanol amines gives better deposition of the siloxane onthe Wool fabric, faster curing and more dependable spray ratings on alltypes of wool fabric. The concentration of the alkanol amine titanatecatalyst relative to the siloxane and the substantive agent is notcritical. Excellent results are obtained, for example, when one employs2% by weight of the substantive agent based on the weight of thesiloxane and an amount of the alkanol amine titanate to give 2% byweight titanium metal based on the weight of the siloxane.

If desired, other resinous materials such as aminoplast resins such asmelamine aldehyde resins, urea aldehyde resins or combinations thereofmay be employed in conjunction with the siloxane.

The treatment of this invention is operative on any type of fabric suchas inorganic fabrics such as glass or asbestos and organic fabrics suchas paper, cotton, wool, rayon, nylon, Orlon, Dacron,polyacrylonitrilevinylchloride copolymers, linen, silk, cellulosetriacetate and leather. The fabrics designated by the terms rayon,nylon, Orlon and Dacron are well known in the textile art. Dacron is asynthetic fiber made by the condensation of dimethyl terephthalate andethylene glycol. Nylon is any of a series of polyamide resins made bythe polymerization of a hexamethylene-diamine salt of adipic acid. Orlonis a synthetic fiber made principally from polyacrylonitrile. Rayon is amanufactured textile fiber or yarn produced from cellulose or with acellulose base.

In carrying out the process of this invention any type of container maybe employed although it is found preferable to use stainless steel sincethere is practically no deposition of the siloxane on the surface of thevessel. Glass or organic plastic vessels can be employed if desired.

The following examples are illustrative only and should not be construedas limiting the invention which is properly set forth in the appendedclaims. Organic radicals in the formulas in this specification are oftenabbreviated by employing the first two letters in the name (i. e. Me formethyl, St for stearyl and Ac for acetic, etc,).

Example 1 An emulsion was prepared which had the composition 600 ml. ofwater, .6 g. of siloxane resinhaving the composition 63 mol percentmonomethylsiloxane, 28 mol percent monophenylsiloxane and 9 mol percentdiphenyl-.

siloxane, .06 g. of an alkyl ether of polyethylene glycol as anemulsifying agent and .012 g. of

30 g. of cotton fabric was immersed in the emulsion and agitated. Theresinous siloxane had completely deposited on the cotton in 60 minutes.

Example 2 Equimolar amounts of ethylenedichloride and diethylenetriaminewere condensed by heating the mixture at reflux. The resulting productwas a mixture of hydrochlorides of ethylene polyimine having about 8ethylene units per molecule.

.012 g. of this material was substituted in the emulsion of Example 1and 30 g. of cotton fabric was immersed therein. The fabric was agitatedand complete deposition of the siloxane resin on the cotton took placein 15 minutes.

Example 3 An emulsion was prepared employing .45 g. of the siloxane ofExample 1, .045 g. of an alkyl ether of polyethylene glycol, .009 g. ofthe imine hydrochloride of Example, 2 and 600 ml. of water. Severalnylon hose weighing a total of 30 g. were immersed in this emulsion andthe siloxane was completely exhausted on the hose in 15 minutes. Thehose were removed from the bath and heated 2 minutes at 220 F. Theresulting hose were snag resistant.

Example 4 An emulsion was prepared employing .6 g. of the siloxane resinof Example 1, .06 g. of an alkyl ether of polyethylene glycol, .06 g. ofthe compound Mes l LHOl 2 H CH HO H having a molecular weight of 736 and600 ml. of water. A 30 gjpiece of cotton fabric was immersed in theemulsion and the siloxane Was completely deposited thereon in 15minutes. The fabric was then removed from the bath and dried and waswater repellent.

Example 5 This example shows the operability of the process of thisinvention over a wide pH range. A series of emulsions were prepared eachof which had the composition .45 g. of the siloxane of Example 1, .045g. of an alkyl ether of polyethylene glycol, .009 g. of a polyethyleneimine having more than 4 ethylene units per molecule and 600 ml. ofwater. The pH of a series of emulsions of this composition was varied byadding ammonia or acidic acid in amounts to give pHs of 2, 4, 6, 7, 8and 10. 30 g. of cotton fabric was immersed in each of these emulsions.In the one having a pH of 2, the silicone was substantially deposited onthe cotton in 30 minutes. In all of the remaining emulsions the siliconewas completely deposited on the cotton in 15 minutes.

Example 6 Example 7 The base siloxane emulsion employed in this examplewas prepared by mixing 100 parts by weight of a 30% emulsion of asiloxane mixture having the composition by weight of a 100 cs. copolymerof trimethylsiloxane and methylhydrogensiloxane and 40% by weight of a10,000 cs. dimethylpolysiloxane fluid, 3.3 parts by weight of a 15%aqueous solution of the polyimine of Example 5 and 10.7 parts by weightof a 20% aqueous solution of sodium acetate. 5.5 g. samples of this baseemulsion were then each diluted with 100 ml. water to give the series ofemulsions employed below. These emulsions were each placed in a glassjar of about 200 ml. capacity and 5 g. of the various fabrics shownbelow were then immersed in the emulsion. The jar was then rotated at 40R. P. M. for 30 minutes. The fabric was then removed from the emulsionand the light transmission of the bath was determined by measuring thetransmission of light at 700 m l. Each sample of fabric was then removedfrom the bath, heated 10 minutes at 150 C. and the spray rating wasdetermined. The results are shown in the table below.

Percent Light Spray Transmission Fabric Rating Initial After 30 Minutes100 6 100 100 3 100 100 4 99 100 8 86 90l00 5 100 4 93 A mixture ofDynel and rayon 100 4 94 Upholstery fabric 100 2 100 Black wool 8Nora-The upholstery and black wool employed gave very low spray ratingswhen the siloxane was applied by the conventional modes of application.

1 Dynel is a copolymer of acrylonltrile and vinylchloride.

Example 8 Equivalent results are obtained when the following siloxanesare employed in the process of Example 7 in conjunction with thefollowing substantive agents.

1 Siloxanes 1 to 3 are copolymers.

Example 9 Wool flannel fabric was treated with the siloxane compositionof Example 7. The siloXane emulsion was employed in amount to give 2% byweight siloxane based on the Weight of the Wool fabric. The emulsion wasadded to a tank of Water along with 2% by Weight of the polyimine ofExample based on the weight of the siloxane and 2% by weight titaniumbased on the Weight of the siloxane, said titanium being added in theform of triethanolamine titanate. The wool fabric was immersed in thetreating emulsion and the siloxane was exhausted on the fabric in 12minutes. The fabric was then removed from the treating bath and cured 9minutes at 200 F. The spray rating was 100.

That which is claimed is:

1. A method of depositing a siloxane on a fabric which comprisesimmersing the fabric in a siloXane-in-water emulsion containing (1) aorgano siloxane of the unit formula in which R is selected from thegroup consisting of monovalent hydrocarbon radicals, hydroxylatedmonovalent hydrocarbon radicals and hydrogen atoms and in has an averagevalue from 1 to 3 inclusive, (2) a non-ionic emulsifying agent and (3)from .2-80% by weight based on the weight of the siloxane of a nitrogencompound selected from the group consisting of polyimines of the formulai" i" z(oHoHtNH),oHoH1z in which Z is of the group consisting of NH;groups and chlorine atoms, R is of the group consisting of hydrogen andmethyl radicals and x has a value of from 4 to inclusive, salts of saidpolyimines and compounds of the formula in which R" is an aliphatichydrocarbon radical of less than 5 carbon atoms, Y is an acid anion andn has a value of from 2 to 6 inclusive and thereafter removing thefabric from the Water and drying it.

2. A method in accordance with claim 1 wherein the organosiloxane is amethylhydrogensiloxane.

3. A composition of matter consisting essentially of a siloXane-in-wateremulsion containing (1) a organosiloxane of the unit formula in which Ris selected from the group consisting of monovalent hydrocarbonradicals, hydroxylated monovalent hydrocarbon radicals and hydrogenatoms and m has an average value from 1 to 3 inclusive, (2) a non-ionic8 emulsifying agent and (3) from .2-% by weight based on the weight ofthe siloxane of a nitrogen compound selected from the group consistingof polyimines of the formula i" F Z(CHCHZNH)=GHCH2Z in which Z is of thegroup consisting of NH groups and chlorine atoms, R is of the groupconsisting of hydrogen and methyl radicals and x has a value of from 4to 20 inclusive, salts of said polyimines and compounds of the formulaNRs-Y HO CHzCHO "H in which R" is an aliphatic hydrocarbon radical ofless than 5 carbon atoms, Y is an acid anion and n has a value of fromto 2 to 6 inclusive.

4. A composition in accordance with claim 3 wherein the organosiloxaneis a methylhydrogensiloxane.

5. A method of depositing a siloxane on a fabric which comprisesimmersing the fabric in a siloXane-in- Water emulsion containing (1) anorganosiloxane of the unit formula R SiO T in which R is of the groupconsisting of monovalent hydrocarbon radicals, hydroxylated monovalenthydrocarbon radicals and hydrogen atoms, at least some of the siliconatoms in said siloxane having hydrogen bonded thereto and m has anaverage value from 1 to 3 inclusive, (2) a non-ionic emulsifying agent,(3) from .280% by Weight based on the weight of the siloxane of anitrogen compound selected from the group consisting of polyimines ofthe formula R! R! Z(( JHCH2NH)z( JHOH2Z in which Z is of the groupconsisting of NH groups and chlorine atoms, R is of the group consistingof hydrogen and methyl radicals and x has a value of from 4 to 20inclusive, salts of said polyimines and compounds of the formula HOCHZGHO "H in which R" is an aliphatic hydrocarbon radical of less than 5carbon atoms, Y is an acid anion and n has a value of from 2 to 6inclusive and (4) an alkanol amine titanate catalyst.

6. A method in accordance With claim 5 in which the organosiloxane is amethylhydrogensiloxane and the alkanol amine titanate is triethanolaminetitanate.

No references cited.

1. A METHOD OF DEPOSITING A SILOXANE ON A FABRIC WHICH COMPRISESIMMERSING THE FABRIC IN A SILOXANE-IN-WATER EMULSION CONTAINING (1) AORGANO SILCOXANE OF THE UNIT FORMULA